AbstractPinking of TiO2‐pigmented PVC can be observed for profiles exposed to the mild environmental conditions of Northern European countries. In this paper, the pinking phenomenon is accounted for at the molecular level by the formation of polyene sequences which are not completely photooxidatively bleached under conditions of oxygen starvation. Photoreduction of TiO2 to give Ti(III) species accounts for greying which cannot be converted into pinking under mild thermooxidative conditions (65°C). The polyenic sequences which account for an initial greying after brief exposure in the SEPAP 12.24 apparatus can be converted into shorter, modified polyene sequences which explain the pinking. From the basic understanding gained, a predictive test has been designed and validated by comparison with results obtained under natural exposure conditions.